Method for converting hydrocarbon gases into liquids



June 25, 1940. 2,205,583

lmao Fon convmurne HYDRocAaon GAsEs INT0 Lmums` Acz. R. WAGNER Filed Nov-122. 1935 f c .mm EN Wav'. M@ dw nw a M1 v f ,11 HMM www l Ratented June 25, 19

i'iED .TATE

METHOD FOR CONVERTNG HYDROCARB GASES INTO LIQUIDS Cary E. Wagner, Chicago, Ill., assignmto The Pure Oil Company, Chicago,I Ill., a corpora tion of Ohio Application November 22, 1935, Serial No. 51,041

10 Claims. (Cl. 19610) This invention relates to method for converting hydrocarbon gases into liquid hydrocarbons, and is more particularly concerned with method for polymerizing olefin-containing gases to liquids boiling within the motor fuel range.

One of the objects of the invention is to provide method for fractionating olefin-containing gases into rich and lean olen fractions and to charge the fractions in any desired proportions to the conversion zone.

Another object of the invention is to provide method for separating the reaction products into a plurality of successively richer olen fractions and for recycling certain selected fractions for polymerization. v l

Another object of the invention is to provide a continuous process for conversion of hydrocarbon gases into liquid hydrocarbons wherein a rich oleflnic gas is segregated and charged to4 the conversion system and to provide for uniform rate of charge by charging sufclent lean vgas to compensate for any deciency of rich gas that may occur from time to time.

Still another object* of the invention is the provision of method for automatically proportioning the recycled fraction in such manner that the richest gas is selectively recycled and only sufficient leaner gas is recycled to compensate for deficiencies in quantity o f richer gas.

Other objects of my invention will be apparent from the following detailed description considered in connection with the drawing, of which The single gure is `a diagrammatic vertical side view of apparatus illustrating my invention.

Referring to the drawing numeral l indicates a line controlled by valve 3 through whichgases, containing oleiinic or other unsaturated hydrocarbon gases, are introduced into the lower portion of an absorber 5. The gases introduced through the line i may be obtained from any suitable source, as for example, gases from a vapor phase cracking plant; or from the stabilizer used for the purpose of stabilizing cracked distillates; or saturated or low olefinic hydrocarbon gases which have been cracked. The gases entering the lower portion of the absorption tower 5 pass in counter-current contact with a liquid absorption menstruum, such as mineral seal oil or other heavy mineral oil distillate, which dissolves oleflnic gases in preference to hydrogen, methaneand saturated gases. The oil enters the top of the tower through the line l. Absorption menstruum is introduced into the system when necessary throuh the line 9 controlled by valve il. tained at a pressure of from to 175 pounds per square inch and preferably between to pounds per square inch. i

Unabsorbed gases leave the top of the absorber throughthe line I3 controlled by valves l5 and I6 and pass out of the system through The absorber is main' the top of this line or through line I1 controlled by valve l1';or a portion may be recycled to the polymerization plantto vbe subsequently described, through the line |48 controlled by valve I9. 4The rich absorption menstruum leaves the bottom of the absorber through the -line 2| controlled by valve 23 and passes into a fixed gaseliminator 24 which may be maintained at a pressure of approximately 135 to 140 pounds per square inch and at a temperature of approximately 100 F. vA portion of the gases absorbed by the menstruum leave the fixed gas eliminator through the line 25 controlled by valves 26 and 21, and these gases may pass to gas storage through the line 28 controlled by valve 29. The

absorption menstruum, with its remaining charge of. absorbed gases, passes from the xed gas eliminator through the line 30 controlled by valve 3|, heat exchanger 33, line 35, and hot oil heater 31 where the rich menstruum is heated to approximately 350 F., and then to the upper portion of'the still 39.

In the still 39 the menstruum is deprived of its charge of gases and light gasoline fractions and these pass overhead through the line 4l and cooler 43 into the gas and water separator 45 which is maintained under substantially the same pressure as the still. The still is maintained at a pressure of about 60 to 80 pounds and preferably about '70 pounds per square inch. The bottom of the still is maintained at a temperature of approximately 340 F. and the top of the still is preferably maintained at about 205 F. A reboiler il is provided for heating the menstruum collected in the mid-portion of the still by circulating the menstruum through the line 5i from the still to the reboiler and thence through the line 69 back to the still. The still is preferably equipped with bubble'plates to obtain good fractionation between the absorption menstruum and the light gases and vapors.

The denuded absorption menstruum is withdrawn from the still through the line 53 and recycled by meansof pump 55 through line 5l controlled by valve 59, the heat exchanger 33,

line 60, and cooler 6l, back to the top of the absorber 5. In the exchanger 33 the hot menstruum passes in indirect heat exchange with the relatively cool rich menstruum in order to partially -ieat the latter and cool the former. Makeup stock is added to the recycled menstruum, when necessary, through the line 9.

Any water that separates out of the condensate in the gas and water separator 45 is withdrawn from the bottom thereof through line 63 controlled by valve 135. Uncondensed gases and vapors leave the top of the gas and Water separator through the line 51 from which they pass into the line 69 controlled by valves 1|, 13 and 15. From the line 69 the gases may pass to storage through the line 11 controlled by valve 19 and through the line Z8; or the gases from line 69 may be charged to the absorber by means of the compressor 30 through line 8| controlled by valve 82, line 83, in which case valves 15 and 13 will be closed; or gases from line 69 may be chargedthrough line 85 controlled by valves 81, B9 and 9|, by means of compressor 93, to the polymerization system to be later described. If

the gases are recycled to the polymerization systern, it will be necessary to close valve 13. It will be evident that by proper regulation of the valves, any portion of the gas may be removed from the system, recycled to the absorber, or sent to the polymerization plant. The portion of the plant to which these gases are sent will depend largely on the capacity of the plant, the volume of gases that are available, and the unsaturated content of the gases.

The condensate from the gas and water separator 45 passes through line 95 to a mixing tank 91 maintained under a pressure of approximately 60 pounds per square inch, where the condensate may be mixed with other condensate introduced through the line 99 controlled by valve IDI. Any gases liberated in themixing tank 91 pass overhead through line |03 and join the gases from the gas and water separator 45 in the line 69. The condensate from the mixing tank is charged by means of pump |05 through line |01 controlled by valve |09, heat exchanger I I I, and line |I3 to the upper part of a fractionating or stabilizing tower H5. A portion of the condensate from the mixing tank 0l may be recycled through the line IIS controlled by valve II1 to the upper part of the still 39, as reflux. The tower ||5 is preferably equipped with bubble plates in order to obtain eflicient fractionation. The tower H5 may be maintained at a pressure of approximately 170 to 210 pounds per square inch. The bottom oi the tower may be preferably malntained at a temperature of 270 F. While the top may be maintained at approximately 165 E. The gases and light vapors pass overhead from the tower 5 through the line IIB and cooler I I9 into reflux accumulator |2i. Any condensate collected in the reflux accumulator I2| is charged back to the top of the fractionator as reflux by means of the pump |23 through line |25 controlled by valve |21'. A hot oil reboiler |29 is provided for maintaining the condensate in the bottom of the fractionating tower ||5 at proper temperature by circulating the condensate through the line itl to the reboiler |29 and passing vapors therefrom back to the fractionatorthrough line |33. The unvaporized condensate or absorption gasoline may be continuously withdrawn from the fractionating tower through the line |35, heat exchanger |I| and line |31 controlled by valve It@ to storage tank I4I. The gasoline which passes to the tank |4I has been weathered and stabilized by having its light ends accusa removed therefrom in the fractionating or stabilizing tower |I5.

The uncondensed gases from the redux accumulator |2| are drawn off from the top thereof through the line |43 controlled by valve |45 and introduced into the line 85 where they may or may not be mixed with gases from line 69, and arethen passed into a tank |41 containing caustic sodasolution for the purpose oi' removing hydrogen sulfide from the gases. When the gases from gas and Water separator 45 and mixing tank 91 are recycled through line 85, gases from fixed gas eliminator 24 may be recycled along with them by closing valves 21 and 10 and opening valve v15. A portion of the gases in line 85 may be removed from the system if desired by passing through by-pass line |48 controlled by valve |48' and rthen through line I1, either through line I3 or 28. The gases are withdrawn from the caustic scrubber |41 through the line |49 and pass into the line |5| where they may be mixed with gases, later to be de` scribed, and the gas mixture passes into the mixing tank |53. The gases are withdrawn from the top of the mixing tank |53 through line |55 by means of compressor |51 and are charged to a heating coil |59 at a pressure of from approximately 500 to 3000 pounds per square inch, but preferably between 600 to 800 pounds per square inch, wherein the gases may be heated to a temperature of from approximately 700 to 1050o F. The heating coil |59 is located in a suitable furnace I6|.

After the gases are heated to the desired temperature in the heating coil |59, they are passed through line |63 to reaction coils |65 which are preferably of larger diameter than the heating coils. If desired, a reaction chamber may be substituted for the reaction coils. Suitable means may be provided for cooling all or a portion of the coils or for insulating any portion of the coils in order to regulate the temperature of the gases therein. In the coils the temperature is preferably maintained within the limits of '100 to 1050 F. for a period of time sufficient to bring about polymerization of a substantial portion of the olenic and other unsaturated gases to liquid hydrocarbons boiling within the gasoline range. Exposure of the gases to reaction temperatures for excessive periods of time should be avoided in order to prevent formation of large amounts of coke and heavy undesirable liquids or tarry matter. The gases leave the reaction coil through the line I 5l and are immediately chilled to a temperature below reaction temperature by means of direct contact with cooling oil introduced through the line |50. The reaction products are preferably cooled to a temperature of approximately 400 to 600 F. The mixture of cooling oil and reaction products then passes through the line I1I, cooler |13, and line |15 to a high pressure accumulator |11. The accumulator v|11 is maintained at approximately reac tion pressure. If, for-example, the pressure of the products in the reaction coils is between 540 to 690 pounds per square inch, the pressure in the'high pressure accumulator may be between 460 to 610 pounds per square inch, the decrease being due to line losses. The products entering the high pressure accumulator are preferably cooled to a temperature of about to 200 F.

The uncondensed gases leave the top of the high pressure accumulator through line |19 controlled by valve Il and may be' eliminated` from the system by passing through the lines Itl and 28. The condensate from the high pressure accumulator passes through the line |85 and conf trol vvalve |81 into low pressure accumulator |89. The pressure in the low pressure accumulator |89 is maintained at approximately 180 to 220 pounds per square inch and the temperature is preferably maintained at about 60 to 180 F. The gases leave the top of vthe accumulator |89 through the line |9| controlled by valve |93 and may be disposed of in four ways. The gases may be removed from the system together with gases from high pressure accumulatorl |11 by passing through line |95 and back pressure regulator |91,

lines |83 and 28; or instead of 'passing out through the line 28, the valve 29 in line 28 may be'closed and the gases passed through line |83 and line |99 controlled by valve 20| and recycled to the absorber 5 together with gas from accumulator |11; or the gases may pass through the line 203 controlled by valve` 205 into the fractionator 2,01; or the gases may pass into the line 209 controlled by valve 2|| into the line 2|3 controlled by valve 2|5 and be mixed with the gases charged to the polymerization plant. It will be evident that by proper regulation of the Valves, gases from the low pressure accumulator |89 may be split and portionsl simultaneously passed to the various places described.

l A portion of the condensate from the low pressure accumulator |89 may be withdrawn through the line 2|1 controlled by valve 2|9 and charged by means of pump 225 through line 22|, controlled by valve 223, and line |69 into contact with the hot reaction products leaving the reaction coils |61 in order to arrest the reaction. The remaining condensate 'from the accumulator |89 may pass through the line 231 controlled by valve 238, heat exchanger 239 and line 24| to the top of the fractionating tower 201 where remaining condensed gases are separatedl and the condensate stabilized. The fractionating tower 201 is preferably maintained at a pressure of approximately 170 to 210 pounds per square inch and the bottom of the tower is maintained at a temperature of from 300 to 340 F. while the top is preferably maintained at a temperature of from 100 to 150 F. If desired, a higher pressure may be maintained in the fractionting tower 201 by inserting'a pump in line 231. A reboiler 243 is connected to the bottom of the fractionating tower by means of lines `245 and 241 in order to maintain the condensate at proper temperature. The unvapori'z'ed condensate may be continuously withdrawn from the reboiler 243 through line 249 and then passed into heat interchange with the relatively cool condensatev coming from the low pressure accumulator |89 in the heat exchanger 239. From the exchanger the condensate passes through line 250 and cooler 25| where it is cooled down to substantially atmospheric temperature and then passed into the storage tank 235.

Instead of utilizing unstabilized condensate from low pressure accumulator |89 as arresting fluid, a portion of the stabilized and cooled condensate from cooler 25| may be charged through line 229 controlled by valve 23|, surge tank 221,.

line 230 controlled by valve 230' to line 22|. If stabilized condensate isused, the valve 2|9 in line 2|1 should be closed.

The gases which are separated in the fractionating tower 201 pass overhead through the line 253 through cooler 255 and line 251 into reflux accumulator 259. The reuxaccumulator is preferably maintained at approximately the same pressure as the fractionating -tower 201 and at a temperature of approximately 60 to 100 F. Any condensate formed in the accumulator 259 is recycled through line 26| controlled by valve 263 by-means of pump 265 tothe top of fractionating tower 201 as reux liquid. The gases from the top of the accumulator 2.59 are withdrawn through the line 2 3 and may be entirely recycled for mixture with the gases in line |49 for charging to the polymerization system; or a portion thereof may flow through line 209 and join the gases from the low pressure accumulator |89.

The valve 2|5 is a metering valve which per-` mits a fixedA volume`of gases to pass through the line '2|3. When it is desired to recycle a xed amount of gas, the metering valve 2 5 is set at the desired amount and any gas from the top of the reflux accumulator 259 in excess of the amount for which the valve 2| 5 is set, passes through the line 209 into the line either back to the absorber through lines 99 and 83 or to gas storage through line 28. If there is a deciency in the volume of gases from the accumulator 259, the deciency is made up by gas from` the low pressure accumulator |89 passing through the line 209 and entering the line 2|3. The back pressure regulator |91 on the line |95 regulates the pressure in line |95 so that the part of the gases from the low pressure accumulator |89"not required to be recycled through lines 209 and 2|3A flow amount is in excess of that for which the valve y 2|5 is set. If it is desired to recycle only gases from reux accumulator 259 to the heating and reaction zones, the valves 2|| and 205 are closed thereby causing' gases from the low pressure accumulator to pass through the line |83 back to the absorber or to gas storage while the total gas from the reflux accumulator 259 is recycled to the polymerization system.

In the preferable method of operation, the gasesfrom the high pressure accumulator |11 are always eliminated from the system through the line 28, and the gases from the low pressure accumulator |89 are used, when necessary, to make up any deficiency in the volume of gases to be recycled to the polymerization unit.

.The composition of the gases that are taken oil? from the high pressure and low pressure accumulators |11 and |89 and from the fractionating tower 201, will depend to-a great extent on the composition of the gas charged to the polymerization system and on the conditions of time, temperature, and pressure to which the gases are subjected in the reaction zone.

In general, the gases tor |11 will be relatively lean in unsaturated and olenic constituents, the gases 01T the fractionator 201 will be relatively rich in unsaturates and olens, and the gases oi the low pressure accumulator |89 will have an unsaturated or olenic content intermediate that of the gases from the high pressure accumulator |11 and the fractionator 201.

As an example, fresh gas, having a specific gravity of 1.124 and containing 55% ofunsaturated hydrocarbons, was subjected to polymerization under pressure of 650 pounds perA squareinch for a period of 58.1 seconds andthe maximum reaction temperature was approximately 985 F. The gas coming off the high pressure accumulator had a gravity of 1.014 and an unsaturated content of 25.6%. The gas off the low pressure accumulator had a gravity of 1.203 and an unsaturated content of 35.6%. The gas off the iractionator had a gravity or 1.491 and an unsaturated content of 49.98%.

As another example, fresh gas, having a gravity of 1.024 and an unsaturated content of 48%, was charged to the polymerization system where it was subjected to a pressure of 650 pounds 4per square inch and a maximum reaction temperature oi 1007" F. for a period of 73.8 seconds.. The gas from the high pressure accumulator had a gravity of 0.856 and an unsaturated content of 24.8%. The gas from the low pressure accumulator had a gravity of 1.052 and an unsaturated content of 33.4%. 'I'he gas off the stabilizer or fractionator had a gravity of 1.274 and an unsaturated content As a third example, fresh gas, having a gravity of 1.11 and an unsaturated content of 54%, was polymerized under 650 pounds pressure and a maximum reaction temperature of 1009 F. The gas off the high pressure accumulator had a gravity of 0.95 and an unsaturated content of 14.4%. The gas ofi the low pressure accumulator had a gravity of 1.22 and an unsaturated content The gas in line ZIS, which was a mixture of the fractionator gas and low pressure accumulator gas, had a gravity of. 1.32 and an unsaturated content of 40.2%.

It will be seen that in accordance with my process, means are provided for recycling al1 of the rich olefin gases from the poly plant fractionator to the heating and reaction zone, and means are also provided for recycling a portion or all of the gases of intermediate unsaturated content to the heating and reaction zone. 'Ihe gases of low unsaturation which are withdrawn from the high pressure accumulator are preferably withe drawn from the system although means are pro vided for introducing this gas together with gas from the low pressure accumulator, into the absorber 5. The high pressure accumulator |71, low pressure accumulator |89, and stabilizer 201 are maintained at pressures gradually decreasing in the order stated. The olenic content of the gases liberated at each stage gradually increases from the stage of highest pressure to the stage of lowest pressure.

' The volume of gases liberated in the fixed gas eliminator 2t is usually small but of relatively high olefin content, usually ranging from 50 to 55% when the gas having an oleiin content of between 40 and 50% is charged to the absorber. The liberated in the gas and water separator t5 will be of comparatively large volume and may have an unsaturated content of from to The gas liberated from the reflux accumulator I2i will be relatively large in volume and will have an olefin content oi approximately to 75%.

It will be seen that by proper regulation of the valves, any proportion of the gas from the low pressure accumulator i789 may be mixed with the gases i'rom the fractionator 201' and recycled to the polymerization system. Likewise, gases from the absorber 5, xed gas eliminator 24, gas and water separator 45, and reflux accumulator 12E, may be mixed in any desirable proportion and charged to the polymerization system. In some cases it is expedient to dilute the highly oleiinic gases from the reflux accumulator I2I with leaner gases before charging to the polymerization system in order to control the reaction. Gases of high olenlc content react violently and have a tendency to form coke and tarry material. By proportioning the high olenic gases with leaner gases, a desired olenic content can be obtained which is most suitable under the conditions of temperature and pressure used.

Although I have described my invention. in connection with the use ot pressures above 500 pounds per square inch, the invention is not limted to operation at these conditions but may be operated at lower pressures and correspondingly higher temperatures.

What I claim is:

1. In a process for the polymerization of oleflnic gases at elevated temperature and under super-atmospheric pressure, the steps of separating unreacted gases from liquid products in three stages wherein the first stage is at substantially reaction pressure and relatively low temperature and the subsequent stages are at progressively lower pressures, recycling a xed amount of gas for admixture with fresh gases charged to the process, and automatically regulating the recirculation from the separating stages so that all the rich oleiinic gas up to said fixed amount is recycled from the last stage and any deficiency in said fixed amount is made up from leaner olenic gases from the second stage.

2. In a process for 'the conversion of olefincontaining hydrocarbon gases into liquid hydrocarbons in a conversion zone at temperatures and pressures suitable for bringing about such conversion, the steps of separating the fresh gas to be converted into at least two fractions, one of which is leaner in olens than is desired in the charging gas and another of which is richer in olefins than is desired in the charging gas. and proportioning the amount of each fraction charged to the conversion zone in order to obtain a predetermined desired oleiin content in the gas charge.

3. In a process for the conversion of fresh olenn-containing gases into liquid hydrocarbons by subjecting gases to suitable conditions of temperature and pressure in a reaction zone, the steps of separating the fresh gas to be converted into at least two fractions, one of which is lean in olens and another of which is rich in olefins,

charging substantially all the rich olelnic gas tol 4. In a process for the conversion of fresh ,ole-

vent which dissolves oleiinic gases in preference to hydrogen and methane, under super-atmospheric pressure, separating the undissolved gases from the solvent, separating the dissolved gases from the solvent in a separate zone, charging substantially all the latter gases to the conversion zone, and adding sutiicient of the undissolved gases to the charge to maintain the charging rate constant.

5. A process for conversion of oleiin-containing gases into liquid hydrocarbons which comprises separating said gases into at least two fractions, one of which is relatively lean in oleiins and the other of which is relatively rich, charging gas at a uniform rate to a heating and reaction zone wherein conditions of temperature and pressure suitable for conversion of gases to liquids are maintained, charging substantially all of the richer oleniclfraction to the conversion zone and charging only a suicient amount of the lean olefinic fraction to maintain the charging rate uniform, separating the gases issuing from accese v the reaction Vzone into at leastl two fractions, one

o f which is lean in olefins and another )of which is rich in oleiins.. Arecycling substantially all the rich gases to the polymerization zone and recycling only sumcient of the lean gas to maintain the recirculation rate constant. v

6. In a process for converting olen-containing hydrocarbon gases to liquid. hydrocarbons under high superatmospheric pressure the steps which comprise separating gaseous fromiiquid reaction products in at least three stages, separating in the first stage gases too low in oleiins to be returned to the process, separating inthe last stage gases rich in oieflns and recycling the same to the process, separating in an intermediate stage gases. having an olefin content between that of the irst and last stage gases and recycling a portion of said gas fromthe intermediate stage for further conversion.

7. The steps in accordance with claim 6 in which the gas from the intermediate stage is fractionated to increase its olen content prior to recycling it to the process. 8. The steps in accordance with ,claim 6 in which gases *from the first and intermediate stages are` fractionated into a fraction of lower oien content and a fraction of higher olefin v content, the lower olefin content fraction is eliminated from'the procs and the higher ole-l iin fraction is recycled for further conversion.

9. The steps'in accordance with claim 6 in which a portion of the gas from the intermediate stage is eliminated from the process.

10. In a process for the conversion of olefin-y containing hydrocarbon gases into liquid hydrocarbons in a conversion zone at temperatures and pressures suitable for bringing about such.A

conversion, the steps of separating the fresh gas to be converted into a gas richer in yoleflns than is desired in the charging'gas and a. fraction leaner in oleiins than is desired in the charging gas, charging all the richer olefin-containing gas to the conversion zone and mixing `with the richer gas prior to conversion thereof sumcient 

